Process for the manufacture of hydrogen and carbon-black.



, H. H. BROWNLEE & R. H. UHLlNGEH.

- PROCESS FOR THE MANUFACTURE 0F HYD-ROGEN AND CARBON BLACK.

APPLICATIQN FILED'MAR. 12. |915.

mwm.

Patented Jan. 18, 1916.

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R. H. BROWNLEE & R. H. UHLINGER. PROCESS FUR THE MANUFACTURE 0F HYDROGEN AND CARBON BLACK. APPLICATION FILED MAR. I2, I9I5.

1,168,931. Patented 12111.18, 19111.

2 SHEETS-SHEET 2.

f ran srarns naar o ROY H. BROWNLEE AND ROY H. UHIJNGER, 0F PITTSBURGH, PENNSYLVANIA, ASSIGNORS TO AMERICN NITRO-PRODUCTS COIVIPANY, 0F PITTSBURGH, PENNSYLVANIA, A CORWRATION Oli DELAWARE.

Specification of Letters Patent.

Patented Jain. 18, i916.

Application led March 12, 1915. Serial No. 14,011

To all @0.7mm it may concern:

Be it known that we, ROY H. BRowNLEE and ROY H. UHLINGER, citizens of the United States, residing at Pittsburgh, inthe county of Allegheny and State of Pennsylvania, have invented certain new and useful Improvements in Processes for theuManufacture of Hydrogen and Carbon-Black, of which the following is a specification.

Our invention consists of an improved method or process of making hydrogen and carbon .black in large quantities at low cost,

and without the use lof complicated or eX- pensive equipment.

Generally stated, the process consists in highly heating a mass of highly refractory material, inthe absence of easily reducible metallic oXids, within a suitable well-insulated containing chamber, and then passing through suchchamber and hot refractory material a suitable hydrocarbon, in the absence of air or other gases, and at a pressure materially above atmospheric pressure. By this means the hydrocarbon is decomposed by coming into intimate contact with the highly heated refractory material, and is thereby decomposed, forming hydrogen and carbon.v By carrying Aout the process under pressure, a much greater efficiency is secured, as for instance, at a pressure of two atmospheres, a furnace of given dimen- Sions will holddo'uble the amount of gas as at one atmosphere, and practically'twice the amount of gas per hour can be decomposed.

The present application-relates to similar subject matter as that of our prior application filed January 21,.1914,O Serial No. 813457. The apparatus shown and described in said application may be employed with good results, or the .modified constructionL .material 5 preferably provided with.A

brick, and near the bottom is a supporting checkerwork 4 of similar material.

A filling of irregular pieces of refractory material 5 is contained within the body of the furnace, above the supporting checkerwork, or the entire inner `part of the furnace may be built up of checkerwork of suitable refractory brick.

At the top of the furnace is a stack 6 provided with a suitable damper valve 7 for valve 11 and a gas pipe 12 having a controlling valve 13,v are introduced to chamber 9 below thevcheckerwork or refractory for heating the furnace and its contents. v

Leading outwardly from the base of the 'furnace 2, at any suitable location, is a conduit 14 provided with an opening and closing valve or damper 15 for controlling the circulation, beyond which the conduit is conne'cted with the tubular conveyer 16. Said conveyer extends through a cooling bath 17 of water within a surrounding lnclosing tank or casing 18, provided with a supply connection 19 and an overflow 20. |1 he other end of the conveying conduit 16 leads to a. receiving hopper 21, provided with an outlet controlling valve 22 at its lower portion for removal of' carbon. At the upper .l end of this hopper 1s a screen box portion,`

between `which and the lower portion of the hopper preferably extends a sloping parti-- tion or shield 22.

v The conduit 16 isprovided with a rotatable screw conveyer 26, actuated by 'shaft 27 driven by any suitable gearing 28, as a pulley or sprocket wheel, whereby to propel the precipitated carbon through the conduit. The vupper screen box portion of the hopper is provided with line screens 30 of cloth or other filtering medium of a suitable nature to filter out the carbon remaining in the hydrogen.` -These screens are preferably the outside of the casing', any collected carbon may be 'dropped into the hopper below.

The outlet at the upper portion of the casing is provided with a suitable'safety valve 24 and a pressure indicating gage 25.

Beyond the screens is a conduit 31 leading toa water seal vessel 32, in which the terminal of the conduit is submerged and conduit 33 leads from the upper portion of water seal vessel 32 to a scrubber 34. of any suitable construction, provided with porousy f material 35 such as coke and a water spray 36, whereby, by means of water, the. gases are cooled and washed. A n additional scrubber 37 may also be provided, connected with theprimary scrubber 34 by a circarbon separator. Such valve is preferably situated betweenthe carbon separator, and

the water seal 32, but may also be insertedy in the line beyond the scrubbers, if preferred, for the same purpose. It will also be understood that the pressure in the furnace 2 may be regulated by valve 15, orv

lower pressures may be regulated by the depth of the end of the conduit 3l. in the water seal 22.

In case nearly. chemically pure hydrogen is required and the available gas or other hyrocarbon, used in the process, contains a considerable amountof nitrogen or other impurities, such as carbon monoXid or' carbon dioXid, it will be necessary to liquefy and rectify the gases from the furnace to remove these impurities, or any other suit'- able method of purification may be resorted to, as required.

' Fig. 2 shows a modified arrangement of Vthe vfurnace 2a whereby the heat of the refractory material leadsdow-nwardly from the top to a suitable outlet 6", gas being` 'furnished by l.pipe 12a having a valve 13L l. and a1r by pipe 10aL having a valve 11. The

gas to be decomposed in such case enters through the base of the furnaceiby pipe 8a,

passing upwardly through the checkerwork x 5a and outwardly at the top through conduit 14a. Said conduit is likewise provided with af controlling valve -15'and a conduit 16!1 extends vertically down within and through a body of water17a in casing 18 provided with a. supply connection 19 and an.over1ow 20a. The lowe'r end of the con duit opens into a hopper 21 of the same.

ing olf the waste water and impurities.

construction as above described, adapted to collect the carbon, the hydrogen passing oif in the same manner and through the same apparatus, similarly indicated by numerals having an exponent a. This arrangement and the operation carried out with the apparatus of F ig. 2 is desirable when hydrogen is the product` required, as this procedure ofpassing the hydrocarbon upwardly under pressure decreases the amount of carbon which is carried over into the conveying conduit, and leaves more in the checkerwork where itis burned during the succeeding Y heating periods.

Fig. 3 shows a suitable apparatus `for 'carvrying out the method with a further or supplemental purification of the hydrogen when it contains carbon monoxid, as is ordinarily thel case. In such arrangement a furnace 2b similar in construction to the furnaces above described having the refractory material or metallic oXids 5b isadapted to receive the hydrogen coming over by pipe 4()b having a suitable controlling valve 40h', from the last scrubber 37, or directly from pipe 33. Said conduit connects'with a'conduit 41 opening into the chamber 9b below supporting checkerwork 4b, and into such conduit 41 is introduced a steam pipe 42 having a controlling valve 43 for the addition of4 steam. Incidentally, a gas pipe 12b having a controlling valve 13", isy introduced into conduit 41, and said conduitis provided with an extension 10b having a valve 11b for inlet of air, whereby to provide for the introduction of fuel and airfor the preheating of the refractory materiaL the products of combustion passing olf by stack 6b having the damper 7". By this means, upon closing circulation of the gases through valve 40" and steam through pipe 42, the checkerwork 5b may be re-heated at the same time as the checkerwork 5 in the primary furnace 2y or 2a is being heated. From such supplemental furnace 2b the gases after passing through the refractory material are led oif by conduit 44 having a1 controlling valve 45, and if desired, acheck valve 46", whereby the hydrogen and carbon dioXid are introduced intothe base ofa cooling tower ,47. Such tower is provided with porous material 35b and a water spray pipe 36", a conduit 38b leading the gases'to one or more additional similar towers, simi-l larly provided with porous materlal and 5 spray 39b for introducing lime water or other alkaline material for the removal of the. carbon dioxid produced in the furnace. The gas passing from the last scrubber by conduit 40bb will beA very' pure hydrogen if.

gas or oilfreesfrom nitrogen is originally used. c The several scrubbers are provided at' the bottom with discharge pipes for carryincensi materials will be greatly impaired, as is well-known; and in the second place, during the heating up period metals, such as copper, iron, etc., will be oxidized, as shown by the following familiar equations.

Then, during the production of h drogen and carbon these oXids will be re uced to reform the metal and carbon monoXid. This is a fact of elementary chemistry.

ln case hydrogenl reduces the copper oXid to formv copper and water, the latter will in turn be reduced by the incandescent carbon in the furnace, so that the final result and also of the use of such is necessarily the addition of carbon monoXid as an impurity to the hydrogen.

The greater the amount of metals or metallic oxids present, the greater will be theproportion of carbon monoXid introduced.

The operation of making hydrogen and carbon black, utilizing the above described apparatus, is as follows, having reference to the apparatus of Fig. 1. With the valve 'l' in stack 6 opened, and valve 15 to the carbon precipitating conduit 16 closed, gas (natural gas, coal gas, oil vapor or other hydrocarbon, preferably as a gas, liquid or volatilizable solid), is admitted through pipe 12 with a suitable amount of air by conduit 10 to chamber 9 below the checkerwork for the complete combustion of the fuel. 'ilhe products of combustion pass upwardly through the interior of furnace 2 and its refractory contents 5, the operation being continued until the furnace and its contents are heated to a very high temperature, c'. e., above the temperature at which the hydrocarbons to be used in the formation of hydrogen and carbon black are decomposed. lhen a suitable temperature has thus been reached, say 14t00o C., or higher, the air supply and then the gas supply is shut off; the stack valve 7 is closed, valve 15 to the carbon precipitator is opened, and. air valve 11 is closed. Then the valves in the pipe or pipes 8 at the top of the furnace are opened, and gas/or other hydrocarbon is introduced at the top of the furnace. rlhe hydrocarbon, passing downwardly in contact with the very highly heated refractory surfaces, and in the absence of air, is decomposed to form hydrogen and carbon black. .'llhese elements pass outwardly from the base of the furnace through conduit 14, entering the conveying conduit 16, being carried there through by conveyer 26 through the cooling water bath 17, effecting precipitation of .the carbon, which is discharged bythe conveyer into hopper 21. The hydrogen gas passing through the automatic pressure regulating valve 1:6,.the water seal tank 32, and the washing tanks 3d and 37, and nnally to the holder, is thus completely cleansed of any suspended impurities. rllhe operation above described is continued vuntil the temperature in the furnace 2 has been reduced to a degree below which entire decomposition of the hydrocarbon will not occur, whereupon the supply of hydrocarbon gas through pipe 8 is shut od at the top of the furnace, after pressure in the furnace is reduced to atmospheric pressure by relieving the regulating valve 46. Valve 15 to the precipitator conduit 16 is then closed, stack valve 7 is opened, and gas and air are again admitted from connections 12 and 10 for additional lcombustion and heating of the refractory without air, so that only minute particles of the carbon will strike the hot checlrerworlr,

by using a suitable atomizer. Otherwise the entire checkerwork would soon be clogged with carbon, whereas, when either a gas or very fine spray is used, the finely divided carbon is carried down with the gas.

lt will be readily understood that much of the carbon will necessarily adhere to the refractory material on the inner walls of the furnace, but by observing the above precautions this will be reduced to a minimum. Such adhering carbon will be consumed in the next heating operation of the furnace.

@wing to incidental traces of moisture in the hydrocarbon used and possible impurities such as metallic oXids in the refractory checkerwork, some carbon monoxid is ordif narily produced during the operation of the furnace.

Where the expression absence of metals or metallic oXids l is used, it is understood to mean the absence of any supplemental or additional amounts of such, and that any such impurities as remain in the hydrogen are only such small amounts as the hydrocarbon may have added to it, or. from the walls of the furnace, or from the refractory material containedA init. j

f conveyer and screen box.

valve 4Gb illustrated in Fig. 3 retains all theA When it is necessary to remove 'the carbon monoXid from the gas, the apparatus illusgases in these chambers vuntil the desired pressureis obtained.

In case We are running the furnace under a pressure of fifteen pounds above atmospheric pressure a considerable amount of gas Will be decomposed before any hydrogen Will -passA through the regulating 'Valve 46 It may be pointed out that the pressure may be regulated either at the valve 15 between the furnace, Fig. 1, and-the conveyer, orby means of the automatic valve' 46 or.46".` When gas begins to pass through I the automatic valve 46, steam is admitted into the furnace shown in Fig'. 8 and the carbon monoXid .in the gas is oxidized to carbon dioXid by means o-f the steam in contact W'ithvthe refractory material or metallic oxids and passes over into the Washing.

tanks Where the carbon dioXid is removed by alkaline materials. i

Where suitable natural gas is obtainable, such as Pennsylvania or West Virginia gas,

vthis process is especially suited for making hydrogen, as each 1000 feet of natural-gas will produce on decomposition over 2100 feet (cubic) of hydrogen. 'When one cubic footof Pennsylvania or West'Virginia natural gas burns in air, somewhat over 1100 B. T. U. (Britishth'ermal` units) of heat are produced, While only 145 B. T. U. are required to break up the -hydrocarbons in a cubic foot of the same gas to form hydrogen and carbon black. This,value, 145 B. T. U.

also includes the heat necessary to raise the temperature of the gas to the temperature at which it Will be decomposed.

What We claim is:

1.The process of making carbon black consisting in decomposing a suitable hydrocarbon by bringing i-t into contact with highly heated refractory material Within an inclosing chamber in the absence of air and at a pressure materially in 'excess of atmosphericvpressur'e, and then separating the carbonfrom the hydrogen.

2. The process of making carbon black consisting in decomposing la suitable hydrocarbon by bringing it into contact with highly heated refractory material Within an inclosing chamber in the absence of air.

and ata pressure materiallyl excess of atmospheric pressure, and then cooling the products to separate the carbon from the hydrogen.

3. The process of making carbon black consisting in decomposing a suitable hydrocarbon by bringing it into '.'contact With' highly heated refractory material Within an inclosing chamber in the absence of air and at a pressure materially in excess of atmospheric pressure, then cooling the products to separate the carbon from theA hydrogen, and thensubjecting the hydrogen to cleans.- ing operations to eliminate impurities.

4. The process of making carbon black and hydrogen consisting in heating refractory material Within an inclosing chamberv by combustion of a suitable fuel therein, and

then passing a suitable hydrocarbon through the chamber at apressure materially in eX- cess of atmospheric pressure and in contact with the highly heated refractory material in the absence of air.

5. The process of making carbon black and hydrogen consisting in heating refractory material Within an inclosingv chamberl by combustionof a suitable' fuel therein, then passing a suitable. hydrocarbon through the chamber at a pressure material-ly in eX- cess of atmospheric pressure and in Contact with the highly heated refractory material in the absence of air', and `then cooling the products to separate thecarbon .from the hydrogen.

6.'The lprocess of makingl carbon black and hydrogen consisting .in heating refrac .tory `material Within an inclosing chamberby combustion of a suitable fuel therein, then passing a suitable hydrocarbon through the chamber at apressure materially in excess'of atmospheric pressure and .in contact With the highly heated refractory material in the absence of air, then cooling the products to 'separate the carbon from the hydrogen, and then. subjecting the hydrogen to suitable treatment for the 'elimination lof impurities. l n v 7. The process of making carbon black andV hydrogen consisting in decomposlng a suitable hydrocarbon by bringing it into contact With highly heated refractory material within van inclosing chamber in the absence of air and at a pressure materiallyin excess of'. atmospheric pressure, then separating the carbon from the hydrogen, then passing the resulting hydrogen and'accompanying carbon monoXid through highly heated refractory material 'in the presence of steam, to oXidizev the carbon monoxid and' then separating the resulting carbon dioxid.

8. The process of making' carbon black and hydrogen consisting in decomposing a suitable hydrocarbon by bringing it into contact with highly heated refractory material -Within an inclosing chamber in the absence of air andat a pressure materially excess of atmospheric pressure, then separating the carbon from the hydrogen, then passing the resulting hydrogen and accompanying carbon monoxid through highly heated metallic oxids in the presence of i steam to oxidize the carbon monoxid, and

then Separating the'. resulting carbon dioxid.

9. The process of making carbon black and'hydrogen consisting in decomposing a suitable hydrocarbon by bringing it' into contact withl highly heated refractory -material within Van inclosingl chamber -in the absence of air and at a pressure materially in excess of atmospheric pressure, then separating the carbon from thje hydrogen, then passing the resulting hydrogen and accomsence of-air and at a pressure materially in excess of atmospheric pressure, then sepa'-, rating thecarbonvfrom the hydrogen, then passing the resulting hydrogen and accompanying carbon monoxid through highly heated metallic oxids at a pressure materially in excess of atmospheric pressure in thepresence of steam to oxidize the carbon monoxid, @nd then separating the resulting carbon dioxid.

11. The process of making carbon black and hydrogen yconsisting in decomposing a. suitable hydrocarbon by atomizing it in convnection with a 'jet of` hydrogen in contact with highly heated refractory material -Within an ,inclosing chamber inthe absence of air and at a pressure materially in excess of t atmospheric pressure, and then cooling the products to separate the carbon from the hydrogen.

12. The process of making carbon black consisting in decomposing a suitable hydrocarbon by bringing it into contact with highly vheated refractory material within an inclos- Iing chamber in the absence of air or metals or easily reducible metallic oxids and at a pressure materially in excess of atmospheric pressure, and then separating the carbon from the hydrogen.

' In testimony whereof we hereunto atHx our signatures in the presence of two wit- ROY H. BROWNLEE. BOY H. UHLINGEE.

` nesses.

Witnesses:

EDWIN O. JoHNs,

W'. A. HECEMAN. 

